Review on demulsification techniques for oil/water emulsion: Comparison of recyclable and irretrievable approaches.

Since the establishment of the first global refinery in 1856, crude oil has remained one of the most lucrative natural resources worldwide. However, during the extraction process from reservoirs, crude oil gets contaminated with sediments, water, and other impurities. The presence of pressure, shear forces, and surface-active compounds in crude oil leads to the formation of unwanted oil/water emulsions. These emulsions can take the form of water-in-oil (W/O) emulsions, where water droplets disperse continuously in crude oil, or oil-in-water (O/W) emulsions, where crude oil droplets are suspended in water. To prevent the spread of water and inorganic salts, these emulsions need to be treated and eliminated. In existing literature, different demulsification procedures have shown varying outcomes in effectively treating oil/water emulsions. The observed discrepancies have been attributed to various factors such as temperature, salinity, pH, droplet size, and emulsifier concentrations. It is crucial to identify the most effective demulsification approach for oil/water separation while adhering to environmental regulations and minimizing costs for the petroleum sector. Therefore, this study aims to explore and review recent advancements in two popular demulsification techniques: chemical demulsification and magnetic nanoparticles-based (MNP) demulsification. The advantages and disadvantages of each technique are assessed, with the magnetic approach emerging as the most promising due to its desirable efficiency and compliance with environmental and economic concerns. The findings of this report are expected to have a significant impact on the overall process of separating oil and water, benefiting the oil and gas industry, as well as other relevant sectors in achieving the circular economy.

Facile Synthesis of Novel Magnetic Janus Graphene Oxide for Efficient and Recyclable Demulsification of Crude Oil-in-Water Emulsion.

Nanoparticles have been widely applied to treat emulsion-containing wastewater in the form of chemical demulsifiers, such as SiO2, Fe3O4, and graphene oxide (GO). Owing to their asymmetric structures and selective adsorption, Janus nanoparticles show greater application potential in many fields. In the present work, the novel magnetic Janus graphene oxide (MJGO) nanoparticle was successfully prepared by grafting magnetic Fe3O4 to the surface of the JGO, and its demulsifying ability to treat a crude oil-in-water emulsion was evaluated. The MJGO structure and its magnetic intensity were verified by Fourier-transform infrared spectra (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and magnetization saturation (MS) tests. Compared with GO and JGO, MJGO displayed the superior efficiency (>96%) to demulsify the crude oil-in-water emulsion, which can be attributed to the reduced electrostatic repulsion between MJGO and the emulsion droplets. Furthermore, the effects of pH and temperature on the demulsification performance of MJGO were also studied. Lastly, the recyclability of MJGO largely reduced the cost of demulsifiers in separating crude oil and water. The current research presents an efficient and recyclable demulsifier, which provides a new perspective for the structural design of nanomaterials and their application in the field of demulsification.

A Novel Demulsifier with Strong Hydrogen Bonding for Effective Breaking of Water-in-Heavy Oil Emulsions.

In the heavy petroleum industry, the development of efficient demulsifiers for the effective breaking of interfacially active asphaltenes (IAA)-stabilized water-in-heavy oil (W/HO) emulsions is a highly attractive but challenging goal. Herein, a novel nitrogen and oxygen containing demulsifier (JXGZ) with strong hydrogen bonding has been successfully synthesized through combining esterification, polymerization and amidation. Bottle tests indicated that JXGZ is effectual in quickly demulsifying the IAA-stabilized W/HO emulsions; complete dehydration (100%) to the emulsions could be achieved in 4 min at 55 °C using 400 ppm of JXGZ. In addition, the effects of demulsifier concentration, temperature and time on the demulsification performance of JXGZ are systematically analyzed. Demulsification mechanisms reveal that the excellent demulsification performance of JXGZ is attributed to the strong hydrogen bonding between JXGZ and water molecules (dual swords synergistic effect under hydrogen bond reconstruction). The interaction of the "dual swords synergistic effect" generated by two types of hydrogen bonds can quickly break the non-covalent interaction force (π-π stacking, Van der Waals force, hydrogen bonds) of IAA at the heavy oil-water interface, quickly promote the aggregation and coalescence of water molecules and finally achieve the demulsification of W/HO emulsions. These findings indicate that the JXGZ demulsifier shows engineering application prospects in the demulsification of heavy oil-water emulsions, and this work provides the key information for developing more efficient chemical demulsifiers suitable for large-scale industrial applications.

Efficient Demulsification Performance of Emulsified Condensate Oil by Hyperbranched Low-Temperature Demulsifiers.

Focusing on the problem of poor demulsification performance of light crude oil emulsions in low-permeability oilfields at low temperatures, the composition of the emulsion samples, clay particle size distribution, and the viscosity-temperature relationship curve of samples were analyzed. Based on the results of emulsion composition analysis and characteristics, the bottle test method was used to analyze the demulsifying effect of different commercial types of demulsifiers, revealing the demulsification mechanism. The field tests confirm the demulsification capabilities of Polyoxyethylene polyoxypropylene quaternized polyoxyolefins surfactants (PR demulsifiers). The results reveal that PR demulsifiers combine the features of decreasing the interfacial tension between oil and water and adsorbing SiO2, allowing for quick demulsification and flocculation at low temperatures. This research serves as a theoretical and practical foundation for the study and advancement of low-temperature demulsification technology in oilfields.

Synthesis and Application of a Novel Multi-Branched Block Polyether Low-Temperature Demulsifier.

In this paper, a low-temperature thick oil demulsifier with high polarity was prepared by introducing ethylene oxide, propylene oxide block, and butylene oxide using m-diphenol as a starting agent. The main reasons for the difficulty involved in the low-temperature emulsification of extractive fluids were explained by analyzing the synthetic influencing factors and infrared spectra of the star comb polymer (PR-D2) and by analyzing the four fractions, interfacial energies, and zeta potentials of crude oils from the Chun and Gao fields. The effects of PR-D2 surfactant on the emulsification performance of crude oil recovery fluids were investigated via indoor and field experiments. The experimental results indicate that the optimal synthesis conditions for this emulsion breaker are as follows: a quality ratio of ionic reaction intermediates and meso-diphenol of R = 10:1; 1 g of the initiator; a polymerization temperature of 80 °C; and a reaction time of 8 h. Colloidal asphaltenes in the crude oil were the main factor hindering the low-temperature demulsification of the Gao oilfield's extractive fluids, and the reason for the demulsification difficulty of the extractive fluids in the Chun oilfield is that the temperature of demulsification is lower than the wax precipitation point. The demulsification rate of the Chun oilfield's extractive fluids reached more than 98% when the PR-D2 concentration reached 150 mg/L at 43 °C. The demulsification rate of the Gao oilfield's extractive fluids reached more than 98% at a PR-D2 concentration of 150 mg/L at 65 °C. The field experiments show that the Chun oilfield's extractive fluids can still demulsify after the temperature is reduced to 43 °C in winter. The emulsification temperature of the Gao oilfield's extractive fluids was reduced from 73 °C to 68 °C, with an excellent demulsification effect.

Synthesis, Performance, Mechanism: A Hyperbranched Phase Reverse Nano-Demulsifier for Condensate Emulsion.

Organic amine and nanosilica were combined to create a nano-demulsifier, which was employed in the oil-water separation process of a condensate emulsion. The nano-demulsifier has the structure of hyperbranched polymers and the skeleton structure of hyperbranched nanomaterials, and displays the demulsification impact of organic amine polymers as well as the synergistic effect of nanomaterials. This nano-demulsifier has the potential to drastically reduce the quantity of condensate demulsifiers utilized in the gathering station. The dehydration rate of the condensate lotion in the gas gathering station can reach more than 95% only at a concentration of 1.0 wt.%. Its application can significantly increase the separation efficiency of the condensate emulsion as well as the quality of condensate oil. It has a positive impact on cost reduction and efficiency in gas well production. The mechanism of action of the demulsifier was also studied, and the results show that the demulsifier is a phase reverse demulsifier.

Screening and Demulsification Mechanism of Fluorinated Demulsifier Based on Molecular Dynamics Simulation.

In order to solve the problem of demulsification difficulties in Liaohe Oilfield, 24 kinds of demulsifiers were screened by using the interface generation energy (IFE) module in the molecular dynamics simulation software Materials Studio to determine the ability of demulsifier molecules to reduce the total energy of the oil-water interface after entering the oil-water interface. Neural network analysis (NNA) and genetic function approximation (GFA) were used as technical means to predict the demulsification effect of the Liaohe crude oil demulsifier. The simulation results show that the SDJ9927 demulsifier with ethylene oxide (EO) and propylene oxide (PO) values of 21 (EO) and 44 (PO) reduced the total energy and interfacial tension of the oil-water interface to the greatest extent, and the interfacial formation energy reached -640.48 Kcal/mol. NNA predicted that the water removal amount of the SDJ9927 demulsifier was 7.21 mL, with an overall error of less than 1.83. GFA predicted that the water removal amount of the SDJ9927 demulsifier was 7.41mL, with an overall error of less than 0.9. The predicted results are consistent with the experimental screening results. SDJ9927 had the highest water removal rate and the best demulsification effect. NNA and GFA had high correlation coefficients, and their R2s were 0.802 and 0.861, respectively. The higher R2 was, the more accurate the prediction accuracy was. Finally, the demulsification mechanism of the interfacial film breaking due to the collision of fluorinated polyether demulsifiers was studied. It was found that the carbon-fluorine chain had high surface activity and high stability, which could protect the carbon-carbon bond in the demulsifier molecules to ensure that there was no re-emulsion due to the stirring external force.

Magnetically recoverable efficient demulsifier for water-in-oil emulsions.

A magnetically recoverable and efficient demulsifier is shown to demulsify surfactant-stable water-in-oil emulsions rapidly. Ferroferric oxide (Fe3 O4 ) particles are firstly coated by amorphous silicon dioxide (SiO2 ), and further functionalized with a commercial dodecyltrimethoxysilane solution (KH-1231). Owing to their paramagnetic properties, the demulsifier particles can be easily recovered with a magnet. Upon addition of demulsifier to emulsions and subsequent sonification, the supernatant becomes completely transparent and no droplets are observed in the micrographs. It was also demonstrated that this demulsifier is effective for emulsions prepared with a variety of oils. Moreover, magnetically recovered demulsifier can be recycled after simple treatment without any decline of efficiency. This work presents a feasible approach for demulsifying water-in-oil emulsions, and has potential value in industry.

Experimental study and machine learning modeling of water removal efficiency from crude oil using demulsifier.

This study deals with the investigation of the water removal efficiency (WRE) from crude oil using a commercial demulsifier. The impacts of time, demulsifier concentration, and temperature on WRE were experimentally studied. The results implied the fact that temperature plays a substantial role in the demulsification and has a direct correlation with WRE. In addition, while increasing the concentration up to 40 ppm contributed to reaching a higher WRE, it did not have positive effects on efficiency at higher concentrations (overdose) and just led to more demulsifier consumption. The concentration dependence of WRE was also diminished at high temperatures. At higher levels of temperature and concentration, the time required to reach a high WRE was noticeably reduced. In order to generalize the findings of this study, the measured experimental data were employed to design predictive methods for WRE based on two smart soft-computing paradigms, including Multilayer perceptron (MLP) and Gaussian process regression (GPR). Despite the high accuracy of both models, the MLP model presented the best consistencies with experimental data with average absolute relative error and relative root mean squared error of 0.84%, and 0.01%, respectively during the testing (validation) step. Also, a visual description through the contour diagram confirmed the capability of the recently proposed models to describe the physical variations of WRE under various operating conditions. Ultimately, a sensitivity analysis based on the MLP model was undertaken to shed light on the order of significance of operational factors in controlling WRE. Overall, the findings of the current research, in turn, have a satisfactory contribution to the efficient design of the water removal process from crude oil based on demulsifiers.

Aromatic poly (amino acids) as an effective low-temperature demulsifier for treating crude oil-in-water emulsions.

Amphiphilic aromatic poly (amino acids) polymers were designed as biodegradability demulsifiers with higher aromaticity, stronger polarity, and side chain-like combs. The effects of demulsifier dosage, structural characteristics and emulsion properties such as pH, salinity, and oil content on the demulsification efficiency were investigated. The results show that the poly (L-glutamic-benzyl ester)-block-poly (L-phenylalanine) (PBLG15-b-PPA15) as the demulsifier can remove more than 99.97% of the oil in a 5.0 wt% oil-in-water (O/W) emulsion at room temperature within 2 min. The poly (L-tyrosine)-block-poly (L-phenylalanine) (PTyr15-b-PPA15) with environmental durability demonstrates high effectiveness, universality, and demulsification speed. It achieves a remarkable demulsification efficiency of up to 99.99% for a 20.0 wt% O/W emulsion at room temperature. The demulsification mechanism indicates that demulsifiers have sufficient interfacial activity can quickly migrate to the oil-water interface after being added to the emulsions. Additionally, when demulsifiers are present in a continuous phase in the molecular form, their "teeth" side chains are beneficial for increasing coalescence and flocculation capacities. Furthermore, according to the Density Functional Theory (DFT) calculations, enhancing the intermolecular interactions between demulsifiers and the primary native surfactants that form an oil-water interfacial film is a more efficient approach to reducing demulsification temperature and improving demulsification efficiency and rate.

Enhanced demulsification of alkaline-surfactant-polymer flooding O/W emulsion by multibranched polyether-polyquaternium based on the size effect of oil droplets.

In the alkaline-surfactant-polymer flooding emulsion, oil droplets with various sizes exhibited different interfacial properties, resulting in different stabilization and destabilization behaviors. In view of this, it is expected to achieve outstanding oil-water separation efficiency by screening targeted demulsifier for oil droplets with different size ranges (0-1, 1-5 and 5-10 µm). Based on the size effect of oil droplets, a series of multibranched polyether-polyquaternium demulsifiers that integrated different charge neutralization and interfacial displacement functionalities were designed by regulating the cationicity and EO:PO ratios. As a result, the most effective polyether-polyquaternium variant for each size range of oil droplet was screened out. By employing these three selected polyether-polyquaternium variants in a sequential batch demulsification test, the maximum demulsification efficiency of 95.1% was obtained, which was much higher than that using a single polyether-polyquaternium variant (82.5%, 80.5% and 83.8%). The adsorption behaviors of polyether-polyquaternium variants on the oil/water interface were investigated by the molecular dynamics simulation. Moreover, the interfacial properties and oil droplet size variations during the demulsification process were monitored, so as explore the demulsification mechanism. This demulsification protocol based on the size effect of oil droplets with its excellent oil-water separation performance offered significant technical promise for the emulsified oil wastewater disposal.

Application of imidazolium based ionic liquids grafted on microcrystalline cellulose as demulsifiers for water in crude oil (W/O) emulsions.

Separation of water and oil from water-in-oil (W/O) emulsion before transportation and refining is very important and critical. Ionic liquids (ILs) and their derivatives have recently attracted much attention as efficient chemical agents for breaking emulsions. So, here, a series of microcrystalline cellulose (MCC) grafted with imidazolium-based ionic liquids (IM-ILs) were synthesized, named as MCC@IM-ILs, and evaluated as eco-friendly surface-active agents for the separation of water from the crude oil. Structure of the synthesized compounds was confirmed by different characterization techniques. Dehydration efficiency percent (DE%) of the synthesized demulsifiers was measured and compared with each other. Synthesized MCC@IM-ILs showed an acceptable DE% to demulsify three kinds of W/O emulsions with different water content after 5 min. Concentration, alkyl chain length, and counter-anion of the synthesized MCC@IM-ILs play a key role in separating water from crude oil. Demulsifier with C10 alkyl chain length showed better DE% than the corresponding demulsifier with C6 alkyl chain length in the W/O (30:70 v/v) emulsion. Also, demulsifier with Br counter anion showed lower DE% than the corresponding BF4 ion-exchanged compound with higher hydrophilicity. Synthesized demulsifiers immobilized on ILs have significant advantages compared to unsupported ILs due to the use of green and economical cellulosic substrate.

Demulsification of amphiphilic gemini ionic liquids and its demulsification mechanism.

This work aims to prepare two new amphiphilic and interfacial active gemini ionic liquids to treat crude oil and investigates its demulsification mechanism. Tetraethylene glycol was pretreated with thionyl chloride and used as a linker to connect succinimide or phthalimide, and then reacted with dodecyl benzene sulphonic acid to obtain the corresponding amphiphilic and interfacial active gemini ionic liquid STA or PTA, respectively. 1H nuclear magnetic resonance spectroscopy (1HNMR) and Fourier-transform infrared spectroscopy (FTIR) was used to determine the chemical structures. The demulsification tests showed the demulsification efficiency with 150 mg/L of STA or PTA at 60 °C for 30 min was 99.89% and 99.79%, respectively. Furthermore, the demulsification mechanism of STA and PTA were studied and the prominent demulsification ability of STA and PTA were attributed to the better interfacial activity and amphipathy which could destroy the asphaltenes interfacial film. These results showed that STA and PTA had excellent demulsification efficiency, which promised application in petroleum industry.

Advances in Automated Piston Liquid-Liquid Microextraction Technique.

A new automated micro liquid-liquid extraction technique was successfully developed. This novel syringe-based technique capitalizes on the advantages of vigorous fluid agitation and the shearing effect of two fluids with different properties to achieve high extraction efficiency. The technique is at least 20 times faster than mechanical shaking or sonication in achieving a similar recovery even with a hydrophilic probe molecule such as 1,4-dioxane in an aqueous medium. Excellent repeatability with a relative standard deviation as low as 0.56% over a five-day test, n = 2 per day, was demonstrated with 1,4-dioxane. Other model compounds in aqueous matrices evaluated, including phenolics and extraction solvents like chloroform and hexane, showed similar performance in repeatability. An added advantage of this technique involves performing multiple extractions. Its capabilities in conducting complicated extraction steps and minimizing the use of organic solvents as low as 200 µL to achieve a preconcentration effect were demonstrated. The technique is suitable for use with emulsion-forming samples without further sample manipulation by incorporating a demulsifier such as acetone during the extraction process. The technique was found to be efficient and environmentally friendly with low solvent waste. This technique is ideal for implementation in automated high throughput and cost-effective quality assurance laboratory environments.

Computational fluid dynamics and factor analysis of a novel swirling demulsified airlift loop reactor for the treatment of refined soybean oil wastewater.

A swirling demulsified airlift loop reactor (SD-ALR) was developed for the treatment of oily wastewater with yeasts. Computational fluid dynamics simulations showed that the gas holdup and liquid velocity gradient in the SD-ALR were 2.9% and 0.37 m/s higher than those in the traditional airlift loop reactor. The optimization results of the swirling demulsifier showed that the optimal number and elevation angle of the blades were 8 and 45°, and the optimal installation position was 150 mm from the bottom of the draft tube. The results of treating refined soybean oil wastewater in the SD-ALR showed that the wastewater treatment time was decreased by 8 h, and the removals of chemical oxygen demand and oil content increased by 5.10% ±â€¯0.02% and 9.55% ±â€¯0.40%, respectively, compared with those in the traditional airlift loop reactor. A volumetric mass transfer coefficient model was established for SD-ALR and oily wastewater.

Mechanisms, performance optimization and new developments in demulsification processes for oil and gas applications.

The present review discusses new developments and optimization of demulsification processes in oil and gas applications, and highlights the critical parameters. Discussed are the primary mechanisms of demulsification, as well as the strategies for developing optimum demulsifiers. Demulsification mechanisms are presented in the context of emulsion stability principles which are equally applicable to the destabilization of crude oil-water emulsions. The present paper is a concise overview of the various surfactant classes and their structure-activity relationship. It correlates demulsification optimization with surfactant properties and their applications. These classes include, but are not limited to pluronic block co-polymers, as well as amine- and siloxane based nonionic surfactants. The emphasis is on providing some strategies for achieving optimum crude oil-water separation efficiency by tuning the demulsifier to the intended application and crude oil properties. A brief overview of unconventional analytical techniques, which reach beyond the standard demulsifier evaluation methods, i.e., Near Infrared Spectroscopy (NIR), and in particular, low resolution NMR relaxometry, highlights their role in monitoring demulsification processes.

Impacts of Acute Exposure of Industrial Chemicals and of Fish (Tilapia Guineensis) Pesticides on The Survival of Fish (Tilpia Guineensis) and Earthworms and Earthworms.

Ecotoxicological effects of industrial chemicals (Rig wash, Oil eater, Nalco, Glycol™) and pesticides (Propoxur, Deltamethrin, Atrazine, Furadan) on Tilapia guineensis (fish) and Aporrectodea longa (earthworms) were tested using the Organisation for Economic Cooperation and Development (OECD) # 203 and 207 protocols. The water and soil ratings indicate that the test chemicals were toxic to the organisms. The estimated 96 hour lethal concentration LC50 values for Rig wash, Oil eater, Nalco EC1304A/COT 505, Glycol, Propoxur, and Deltamethrin were 26.34±0.46, 6.02±0.30, 3.07±0.14, 1.31±0.01, 20.91±0 and 0.01±0 mg/l respectively. In the earthworm bioassay, the estimated 14-day LC50 values for Rigwash, Oil eater, Nalco EC1304A/COT 505, Glycol, Atrazine and Furadan were 80.05±3.5, 151.55±10.7, 172.63±14.2, 63.72±2.43, 4.97±0 and 0.29±0 mg/kg respectively. Safety factors are arbitrarily built in around the LC50 values in order to arrive at environmentally tolerable concentrations. The concentration of a chemical in the receiving environment should not exceed 10% of the LC50. The organisms exposed to the test chemicals showed significant difference when compared with the levels measured in the control group. The observed sensitivity of the test organisms to the chemicals indicates that adherence to standard safety limits/measures should be maintained during use and disposal of hazardous chemicals. This would ensure that the biotic components of the Nigerian Niger Delta ecosystem are prudently protected.